(24) (25). Sulfur compounds appear to enhance conversion (26) (27). To promote WGS, homogeneous catalysis with caustic (28) and Fe(CO)5 (29) have been used. In these complex systems, interactions among reactants with catalysts as well as with each other occur, often adverse. For example, using compounds modeling coal functionalities, Takemura et al found that without CO, both Mo and W catalysts promoted C-C bound cleavage, but with CO, only W was effective for cracking (30). Many of these studies were directed toward reaction paths and intermediates (31) and showed that H2 and CO were not the only reductants, rather, other intermediates such as formate ion were also present.
Liquefaction of woody biomass in aqueous medium occurs fairly rapidly between 200 and 300oC. particularly in acidic or basic conditions. Anderson and Wiser have reviewed pioneering work on pyrolysis and hydrogenative (including CO/H2O) conversion of waste biomass (32) Ligno-cellulosic reactions (plant derived matter) are compactly summarized by Chum and Baiszer (33). Antal has found that pyrolysis of biomass in steam at atmospheric pressure produces hydrocarbon rich synthesis gas and much char (34). Cellulose in water at 270oC in basic conditions gives 34% conversion based on carbon (35). Addition of CO enhances the liquid yield. One literature report indicates CO/H2O liquequefaction of cellulosic pulp in the presence of Ru3(CO)12 and base produces a high quality oil in 98-99% yield (36), and bagasse (sugarcane waste) was reduced by formate (which can arise from CO/H2O) at 350oC in water (37). Other waste materials, especially lignin containing and glycosidic wastes, are also reactive under these conditions (38) and are feasible candidates for coal and kerogen co-processing feeds in aqueous systems. These processes generally leave some residual carbonaceous char as one reaction product.
Although these hydroxylic materials will normally char in pyrolysis, Modell has shown that in H2O (SC) these materials cleanly decompose (39) (40). This approach is being explored actively at Sandia, at Texaco and at U. of Texas Austin, among other places. Not only does the WCR eliminate char, it also converts (detoxifies) hazardous matter as halogenated organics to produce water soluble salts. A recent patent claims the use of a biomass carbon source such as a carbohydrate to promote base catalyzed decomposition of organics, both halogenated and non-halogenated, in aqueous media above 200oC (41).
Organic Reactivity in the Water Critical region (WCR) has not been extensively explored. Although strictly, the water critical region lies above the water critical point, Tc= 374o C,, Pc= 218 atm., c= 0.31 g/ml, solubilities depend upon density of the fluid phase as well as temperature and the chemicial nature of the fluid. Consequently, the aqueous liquid phase below Tc similarly shows enhanced solubility of both ionic solids and hydrocarbon substrates. Similarly, the aqueous non-condensable fluid appreciably above Tc retains its solvency of inorganics, solvates them, and even ionizes them provided the water density ( partial pressure) remains liquid-like, say 0.3 g/ml. Further, solutes, both polar and non-polar, alter the phase structure so that the "critical' region is band about the pure substance Tc. For these reasons, the concept of a water critical region is more realistic than "supercritical water".
For aqueous SC fluids, the temperature range of the WCR is one in which many organics thermally transform or decompose, conversion in aqueous media began to stimulate interest in '60s. In that period, the relatively high solubilities of both organic and inorganic materials in the WCR (300-450oC) were systematically examined (42) (43) (44). Interest in applications supercritical extraction (45) with water as well as other fluids arose from this work.
At Amoco Oil Co., conversion to and extraction of liquids in WCR was examined for coals (about
30% ash free basis at 400oC (46)
), shales (90% a.f. above 375oC (47) ) and tar sands. With coal, liquid
production in the aqueous system was about the same as that in toluene or other non-donor solvent.
However, with shale, coal and tars, the normal gaseous products of dry pyrolysis -- light olefinic gases,
H2S, COS -- were largely absent in the aqueous system indicating that some non-pyrolytic chemistry was
occurring in the WCR. An additional benefit was that residual coal and shale mineral solids were
relatively easily separated from the heavy oils very likely because of modification of the asphaltenic
content of the products. These results pointed to a reductive environment although no added hydrogen
was present. Subsequent work (48) (49) (50) (51) on low and mid-rank coals has extended Amoco Oil results and
generally demonstrated higher coal liquid yields with or without hydrogen although the conversions were
too low to compete with donor systems. Winters, Lewan and others applied these results to evaluation of source rocks and showed that
water in the range 300-350oC effectively extracted oils from shales still without formation of olefinic
material characteristic of dry pyrolysis (52) This methodology, termed hydrous pyrolysis, has become
widely used by geochemists to simulate petroleum generation potential and quality. Reaction paths and reactivities in aqueous systems in the critical region have been reported in
recent years for pure compounds modeling coal and shale kerogen functional group types. Klein has
reported pyrolyses of benzyl ethers at 350-400oC in dense water noting that the products and product
yields differ somewhat from those of non-aqueous pyrolysis (53). Several groups (54) (55) (56) have determined
reactivities of several organics in super-critical water which have suggested that multiple pathways in
addition to simple homolytic are operating. Recently, Siskin, Katritsky, and co-workers produced an
exhaustive survey the aquo-chemistries of acyclic, carbocyclic, and carbo-heterocyclic compounds in the
range 250 to 350oC (57) (58) (59). The latter workers report high conversions, for example, of olefins, alcohols,
aldehydes and aliphatic ethers in water at 250oC with product patterns characteristic of ionic reactions.
Above 350oC, they find free radical derived thermolytic products approaching par with those from ionic
paths and suggest that water would have less effect on product slates at higher temperature. However,
they do not report pressure effects and in the (poorly delineated) critical region of a complex water
hydrocarbon mixture, the relative stabilization of
ionic intermediates would depend strongly upon
the density, and therefore pressure, of the
system. This is an area which deserves further
attention. At Amoco Oil Company in the early '70s an
investigation of the reactivity of resids and
bitumens in supercritical water revealed that the
quality of heavy oil products was improved in the
presence of group eight metal salts (60). For
example, treatment at 400oC in an aqueous fluid
(fluid density ca. 0.3 g/ml) containing ruthenium
chloride, increased the H/C atom ratio of a Texas
vacuum resid (1.43 to 1.52) and of a topped
Athabasca bitumen (1.46 to 1.48). These results
pointed to a reductive environment although no
added hydrogen was present. With a high sulfur
resids and tar sands oils, 50-80% metals
removal(Ni,V) and 70-80% desulfurization coud
be achieved. From an IL#6 coal, 55% overall
desulfurization was realized in liquids and recovered solids. (61), In this work, olefins were found to react facilely in the WCR. Thus, hex-1-ene, in addition to
isomerizing rapidly to its internal isomers, gave hexane, pentane and CO2 (very small amounts of
hexan-2-one and hexan-3-one also formed). In the presence of dissolved ruthenium or rhodium salts,
the hexenes were converted almost quantitatively n-hexane and n-pentane in a 2/1 mol ratio with CO2
accounting for the missing carbon. Hexan-1-ol and hexaldehyde gave the same paraffinic products
indicating that the olefin reacts by hydration, dehydrogenation, decarbonylation, and the shift reaction to
give pentane and two mols of hydrogen (actual or virtual) which appears as hexane. The activity of
dissolved salts in this process, shown as hexane yield in a 2 hr experiment at 350oC in the figure to the
right, peaks sharply for ruthenium and is small for 3rd row salts. liquefaction in methanol and methanol-water might similarly involve alkoxides.
Ross and Blessing have discussed hydride transfer as a reducing path in alcohol systems (66). Other oxides as MnO2 or TiO2 were poor catalysts but had a promotional effect with the group eight
metals. kThe graph shows that for hexene to hexane sequence, the activity of metal oxide promoted
ruthenium catalysisrelative to to neat Ru ion (kprom/kneat) is quite substantial MnO2. Very likely, these
oxides are also dissolved in the WCR, but their function is not known. Probing experiments showed that
toluene and benzaldehyde with Ru in SC water gave benzene and CO2 analogously to the olefin
process. These unsaturate reactions thus might be a source for the reducing environment in the
aqueous SC region which could be used syn-fuel conversions. High reductive capacity of glucosidic biopolymers based on the
alcohol and aldehyde chemistries with metal catalysts in the aqueous critical region might therefore be
anticipated. Recently, stilbene was found to be reduced by glucose in an aqueous solution of RuCl3 at
350-375oC (McCollum, unpublished observation). From these backgound considerations, use of ligno-cellulosic bio-waste as a reductive material with coal
appears to have industrial potential. Some attractive aspects include: 1. It is a relatively high value application of the waste. 2. It's reductive potential is thermodyamically high if suitable reaction paths are found. 3. The waste material has already been collected for other processing or more likely, disposal purposes. 4. The waste is a renewable resource, i.e., it is CO2 neutral to the environment. 5. The approach can probably convert most non-reused wastes to assets. 6. Sufficient ligno-cellulosic biowaste is generated in the U.S. to co-process a significant fraction of the annual coal production. 7. Reactions in the WCR will detoxify contaminants introduced with both the waste biomass and the hydrocarbon co-feed. There are also areas of concern including: 1. A successful process will probably require high pressure vessels, but compression would be
either autogenous (batch system) or hydrostatic (flow system) eliminating the need for gas
compression. 2. Catalyst retention, either by fixed bed or
by recycling of active sludge would be required, if
expensive catalysts prove
necessary. 3, To minimize transportation costs, syn-fuels processing plants and biowaste collection
points should be reasonably close. The technical proposal drawn from these results embraces aqueous co-processing ligno-cellulosic wastes
together with bitumens, refinery resids,and low H/C coal or shale kerogens (particularly "Type II"
kerogens) Key features are the need for a liquid-like fluid density in the aqueous critical region and use
of group eight metal catalysts in a high pH environment to direct decomposition of the biopolymers. d2. Anticipated Results Processes optimized for liquefying and/or upgrading variously coal synfuels, shale concentrates, and
very likely, tar sands bitumens and refinery vacuum resids should ultimately emerge from this project.
The processes should operate at milder temperature/time severities compared with conventional
processing but will employ higher (hydrostatically generated) pressures. Conversion of wastes to useful and environmentally benign products will provide a valuble alternative to
waste management planners and firms. Although the processes will pull in the time frame for shale and
particularly coal liquefaction costs reach parity with petroleum, probably they will be of immediate
interest to oil refiners for treating resids. They will also provide a valuable outlet for waste material
otherwise causing disposal problems and thus be attractive to waste management firms. Sugar cane or
corn product manufacturers could also use the approach as an outlet for using their wastes. Fuel
applications for municipal waste are already being examined and use here would be a prominent
candidate as an alternative route. Because catalysts compatible with WCR conditions will be
unconventional, catalyst manufacturers will have to supply a new market built around WCR processing.
A number of small companies and University projects dealing with SC fluid processes (e.g., Modek
Corp., Phasex Inc., U. Texas-Austin) would have an interest in promoting this work. d3. Significance of Phase I Effort Since relatively little work has been reported on reactivity and reaction paths of bio-matter under these
conditions, and this chemistry will necessarily need to be emphasized in phase I, but "proof of concept"
experiments with representative synfuels and cellulosic reductants will be done, These and a preliminary
economic scoping will would form the basis for a phase II proposal. In phase II, a catalyst development program would be initiated to determine activity, sensitivity to
inhibitors, catalyst robustness and life or recovery and recyclability. We would also explore reactor
configurations (batch, stirred tank, slurry flow) and feed systems and carry out bench scale
demonstrations. Investigation of the chemistry of the conversion reactions would be continued through
this period to guide catalyst development. Economic projections based on bench scale data would be
done. e. Phase I Technical Objectives Phase I will emphasize the chemistry of ligno-cellulosic matter in the WCR in the presence of group 8
metal ions, particularly that related to hydrogen transfer to hydrogen deficient materials. Both model
compounds and representative coal and shale kerogens will be used as hydrogen acceptors. Questions we need to address include: 1. Establishing the nature of H-transfer from simple and polymeric glucosides to acceptor models for hydrogenation and for hydrocracking unsaturates and polyhydroxy aromatic materials. 2. Conducting a variables study (T, time, [reactants]/water ratio, [catalyst]). 3. Screening catalysts (does order found for olefins hold?). 4. Testing effectiveness of different bio-mass types. 5. Examining interactive effects with sulfur and nitrogen (not strong in olefin and resid work). 6. Doing "proof-of-concept" tests with coal and shale kerogens with cellulosic materials. 7. Economic scoping to identify cost sensitive aspects needing attention in further concept
development. f. Work Plan- Phase I We propose to examine the experimental questions using small-scale tubing (Neavel type) reactor batch
experiments. Several experiments at once can be carried out using a sand bath heater. Model
compounds will be used to define reactions involved in cellulosic decomposition and interaction with
hydrogen acceptors. Specifically, we propose to examine: 1. Reaction of glucose, a reducing and a non-reducing disaccharide, and cellulose, anisole and
guiacol (models to assess ether cleavage and
de-oxygenation in lignin like models) in water at
two temperatures (e.g.275 and 350oC, two
reaction times, neat and with Ru, at autogenous
and basic pH. 2. Reaction of cyclo-octene (to reduce side
reactions which in acyclic olefins compete with
saturation) to establish the hydrogenation-dehydrogenation equilbium with glucose under
the above conditions. 3. Screening group 8 metal salts with cyclo-octene under a condition set selected from step 2. 4. Examine reactions of n-nonylbenzene (for side-chain cracking) and 2-n-hexyltetralin (for
aromatic dehydrogenation-cracking) with Ru and glucose at a condition set selected from step 2. 5. Examine reactants of step 4 and of cyclo-octene with Ru and glucose with Mo, W and Mn
oxides to determine promotional effect on cracking and hydrogen-transfer. 6. Examine conversion of pulped paper as a ligno-cellulose at conditions selected from model
compound runs. 7. Proof-of-concept runs of pulped paper with above syncrude types.. Some areas which should be examined in any continuing work include total pressure effects, a two-phase solvent system such as water/toluene, and other biowastes potential reductants. Based upon the proof-of-concept experiments, a scoping economic evaluation will be done to determine
order of magnitude cost and more importantly at this stage, to identify the most cost sensitive areas
which require attention in any further work. g. Project Description - Phase I 1. Project Objective The applicant shall study the chemistry of catalysed decomposition of ligno-cellulosic and derivative
matter in the water critical region (WCR) and its interaction with hydrogen deficient substrates, first
model compounds and then synfuels. These results will initiate design of a process for utilising biowaste
as an effective hydrogen donor for liquefying and upgrading coal and shale kerogens. 2. Project Description The work to be performed consists of the following tasks: 1. Assembly of mini-reactor system for small scale batch work. 2. Study of behavior of ligno-cellulosic materials with Ru salts in the WCR and of hydrogen transfer
from these systems to model olefin and aromatic acceptors. 3. Multi level process variable study of the glucoside donor-unsaturated acceptor processes. 4. Screen group 8 metal salts for hydrogen transfer activity and screen group 5, 6, and 7 metal oxides
as promoters of hydrogen and transfer. 5. Conduct proof-of-concept co-conversions of coals and shale kerogens with biomass and biomass
waste (e.g. paper) in the WCR. 6. Conduct a scoping economic study of a conceptual process cost and to identify the most cost
sensitive aspects of it. 7. Prepare Final Report. 3. Perfomance Schedule Task 2.1 will be completed within one month after start of work. Task 2.2 will be completed within two months after start of work. Task 2.3 will be completed by three months after start of work. Task 2.4 will be completed by four months after start of work. Task 2.5 and 2.6 will be completed by five months after start of work. Task 2.7 will be completed by six months after start of work. h. Related Research Dr. John D. McCollum, principal investigator of the proposed project, has worked on several aspects of the three synfuel sources, coals, shales and tar sands since 1973. Initially,
the work focused on conversions in water in its critical region; ten patents were generated from this
effort. For several years, he was concerned with a chemical approach to concentration of hale kerogen,
work from which two patents issued. Most recently, he has been concerned with approaches to moderate
severity liquefaction of coal and shale kerogens based upon the nature of the crosslinks of the
macromolecules. A patent application based upon this work is pending. Earlier in his career at Amoco,
Dr. McCollum was active in mass spectrometry, a field which has proven valuable as GC-MS evolved to
a potent analytical tool for synfuels. Dr. Ken Robinson, key team member of the proposed project, has been deeply involved in numerous
coal liquefaction and other synfuel projects for the last 16 years. He has been successful in obtaining a
patent for the Amocat family of liquefaction catalysts used in some of the H-Coal program at
Catlettsurgh, KY. Dr Rodney Mieville, the other key team member, has been intimately involved in the science of
adsorption, since the start of his technical career. He has studied adsorption on reforming catalysts,
molecular sieves and more recently was involved in a unique adsorbent system emission control of
automobiles during cold-start. He is well qualified to participate on the research team on this project and
is currently involved on developing drinking water carbons under an SBIR grant from the EPA. i. Key Personnel Dr. John D. McCollum (Principal Investigator) Ph.D. Organic Chemistry, 1957, Harvard University A.M. Organic Chemistry, 1951, Harvard University B.S. Chemistry, 1949, University of Illinois Experience- 1990-present: Consultant Synfuels Consultant in synfuel chemistry. 1988-1989: Amoco Oil Company Research Associate Exploratory research on resid and bitumen thermal chemistry. Project leader, biomimetic methane
oxidation. 1986-1988: Amoco Corporation Research Associate Kerogen structural features and reactivity; organic geochemistry. 1982-1985: Amoco Oil Company Research Associate Oil shale beneficiation, liquefaction. Organic-mineral bonding in and mineral separation from coals,
shales, and tar sands. 1966-1981: Amoco Oil Company Project Manager Cool plasma and aqueous super-critical hydrocarbon chemistry. Shale, coal, biomass liquefaction,
microbiological desulfurization and denitrogenation. 1960-1965: Amoco Oil Company Senior Project Chemist U.S. Government contract research in radiation chemistry (Air Force) and fluorine oxidizer chemistry
(ARPA). 1953-1959: Standard Oil Company (Indiana) Project Chemist Platinum catalytic reforming. Organic mechanistic mass spectrometry. Fellow, American Institute of Chemists; member, American Chemical Society, Chicago Catalysis
Society. 19 Patents, 10 publications, a book chapter. Publications: E.R. Alexander, M.R. Kinter, J.D. McCollum, "Mechanism of Formation of Dibenzoylfurazane Oxide from
Phenylmethylcarbinol", J. Am. Chem. Soc. 1950, 72, 801. E.R. Alexander, J.D. McCollum, D.E. Paul, "Synthesis of Ethyl t-Alkyl Cyanoacetates", J. Am. Chem.
Soc. 1950, 72, 4791. P.D. Bartlett, J.D. McCollum, "Hydride Transfer Mechanisms in Strongly Acidic Media. Reduction of
Carbonium Ions by Alcohols and Evaluation of the Basic Strength of i-Propyl Alcohol", J. Am. Chem. Soc.
1956, 78, 1441. S. Meyerson, P.N. Rylander, E.L. Eliel, J.D. McCollum, "Organic Ions in the Gas Phase. VII. Tropylium
Ion from Benzyl Chloride and Benzyl Alcohol", J. Am. Chem. Soc. 1959, 81, 2606. J.D. McCollum, S. Meyerson, "Hydrogen Migration in Gaseous Organic Cations", J. Am. Chem. Soc.
1959, 81, 4116. S. Meyerson, J.D. McCollum, P.N. Rylander, "Organic Ions in the Gas Phase. VIII. Bicycloheptadiene", J.
Am. Chem. Soc. 1961, 83, 1401. E.L. Eliel, J.D. McCollum, S. Meyerson, P.N. Rylander, "Organic Ions in the Gas Phase. IX. Dissociation
of Benzyl Alcohol by Electron Impact", J. Am. Chem. Soc. 1961, 83, 2481. S. Meyerson, J.D. McCollum, "Organic Ions in the Gas Phase. X. Decomposition of Benzaldehyde under
Electron Impact", J. Am. Chem. Soc. 1963, 85, 1739. P.N. Rylander, S. Meyerson, E.L. Eliel, J.D. McCollum, "Organic Ions in the Gas Phase. XII. Aniline", J.
Am. Chem. Soc. 1963, 85, 2723. S. Meyerson, J.D. McCollum, "Mass Spectra of Organic Molecules", in Advances in Analytical Chemistry
and Instrumentation, C.N. Reilly, Ed., Interscience Publishers, New York, 1963, v. 2, ch. 2. J.D. McCollum, W.F. Wolff, "Chemical Beneficiation of Oil Shale", Energy Fuels 1990, 4, 11. Patents: J.R. Coley, B.L. Evering, J.D. McCollum, "Hydroforming Light Naphtha", US 2,861,964. P. Fotis, J.D. McCollum, "Hydrogenation Method", US 3,324,018. J.F. Connolly, R.F. Flannery, J.D. McCollum, "Electroreduction of Aromatic Compounds to their 1,4-dihydro Derivatives", US 3,699,020. J.D. McCollum, L.M. Quick, "Process for Recovering and Upgrading Hydrocarbons from Oil Shale and
Tar Sands", US 3,948,754; US 3,958,755. J.D. McCollum, L.M. Quick, "Process for Upgrading a Hydrocarbon Fraction", US 3,960,706; US
3,960,708; US 3,989,618. J.D. McCollum, L.M. Quick, "Process for Recovering Upgraded Products from Coal", US 3,983,027; US
3,983,028; US 3,988,238. J.D. McCollum, L.M. Quick, "Process for Recovering and Upgrading Hydrocarbons from Tar Sands", US
4,005,005. J.D. McCollum, L.M. Quick, "Process for Recovering and Upgrading Hydrocarbons from Oil Shale", US
4,151,068. J.D. McCollum, "Method for Detecting Underground Conditions", US 4,199,026; US 4,266,608. I. Ginsburgh, J.D. McCollum, "Method for Detecting an Underground Flame Front Using Resistence
Probes", US 4,210,868. I. Ginsburgh, J.D. McCollum, "Induction Coil Method for Detecting an Underground Flame Front", US
4,210,867. W.F. Wolff, J.D. McCollum, "Method for Treating Shale", US 4,584,088; US 4.668,380. Dr. Ken Robinson (Team member) D.Sc. Ch.E. 1970, Washington University-St. Louis M.S. Ch.E. 1964, University of Michigan B.S. Ch.E. 1963, University of Michigan Experience- 11/89 to 4/92: Amoco Corporation Manager, Technical University Relations Technical liaison with major universities in the United States. Technology transfer and coordination of
external research. 11/84-01/89: Amoco Oil Company, Research and Development Research Associate Exploratory process research on heavy oil conversion, asphaltene solubility-solids formulation, and coal-resid coprocessing. 01/80-11/84: Standard Oil (Indiana) Director, Coal Utilization 01/73-01/80: Amoco Oil Company, Research and Development Project Manager Petroleum Refining Research and Synfuels 1/65-1/73: Monsanto Company Senior Development Engineer Member of AIChE, ACS, Chicago Catalysis Society Professional Engineer in Illinois 5 Patents, 14 Publications Publications: 1. K. K. Robinson, and D. E. Briggs, "Isothermal Pressure Drop Across Banks of Finned Tubes," Heat
Transfer-Los Angeles, Chemical Engineering Progress Symposium Series, Vol. 62, No. 64, 177
(1966). 2. K. K. Robinson, A. Hershman, F. E. Paulik, and J. F. Roth, "Catalytic Vapor Phase
Hydroformylation of Propylene Over Supported Rhodium Complexes," JOURNAL OF CATALYSIS,
Volume. 15, No. 3, 245 (1969). 3. A. Hershman, K. K. Robinson, J. H. Craddock, and J. F. Roth, "Continuous Propylene
Hydroformylation in a Gas Sparged Reactor," INDUSTRIAL AND ENGINEERING CHEMISTRY,
PRODUCT R&D, Vol. 8, No. 4, 372 (1969). 4. K. K. Robinson, and E. Weger, "High Temperature Pyrolysis of Propylene-Propane Mixtures,"
INDUSTRIAL AND ENGINEERING CHEMISTRY FUNDAMENTALS, Vol. 10, No. 2, 198 (1971). 5. K. K. Robinson, A. Hershman, J. H. Craddock, J. F. Roth, "Kinetics of the Catalytic Vapor Phase
Carbonylation of Methanol to Acetic Acid," JOURNAL OF CATALYSIS, Vol. 27, No. 3, 389 (1972). 6. E. C. Meyers, and K. K. Robinson, "Multiphase Kinetic Studies with a Spinning Basket Reactor,"
ACS Symposium Series No. 65, Chemical Reaction Engineering 37 (1978). 7. J. A. Mahoney, K. K. Robinson, and E. C. Myers, "Catalyst Evaluation with the Gradientless
Reactor," CHEMTECH, 758 (December 1978). 8. R. J. Bertolacini, L. C. Gutberlet, D. K. Kim and K. K. Robinson, "Catalyst Development for Coal
Liquefaction," EPRI, AF-574 (1977). 9. R. J. Bertolacini, L. C. Gutberlet, D. K. Kim, and K. K. Robinson, "Catalyst Development for Coal
Liquefaction," EPRI AF-1084 (1979). 10. D. K. Kim, R. J. Bertolacini, J. M. Forgac, R. J. Pellet, and K. K. Robinson, "Catalyst Development
for Coal Liquefaction," EPRI AF-1233 (1979). 11. D. F. Tatterson, K. K. Robinson, T. L. Marker, and R. Guercio, "Coal Flash Pyrolysis in a Free-Jet
Reactor," I&EC RESEARCH, 27 1606 (1988). 12. K. K. Robinson "Molecular Structure of Heavy Coal Liquids," EPRI ER-6099-SR (1988). 13. R. J. Bertolacini, J. M. Forgac, D. K. Kim, R. J. Pellet, and K. K. Robinson "Catalytic Functionality
for Cool Hydroliquefaction," Third International Conference--The Chemistry and Uses of
Molybdenum (1979). 14. D. F. Tatterson, K. K. Robinson, R. Guercio, and T. L. Marker, "Feedstock Effects in Coal Flash
Pyrolysis," Communication, I&EC, (1990). Patents: 1. F. E. Paulik, K. K. Robinson, and J. F. Roth. "Vapor Phase Hydroformylation Process," US 3,487,112-British Patent 1,228,201. 2. D. K. Kim, R. J. Bertolacini, L. C. Gutberlet, and K. K. Robinson, "Process for Coal
Liquefaction and Catalyst," US 4,257,922. 3. D. K. Kim, R. J. Bertolacini, L. C. Gutberlet, and K. K. Robinson, "Process for Coal
Liquefaction and Catalyst," US 4,294,685. 4. J. S. Meyer, K. K. Robinson, J. M. Forgac, and D. F. Tatterson, "Rapid Hydropyrolysis of
Carbonaceous Solids," US 4,326,944. 5. K. K. Robinson, "Granulated Activated Carbon for Water Treatment," US 4,954,469. Dr. Rodney L. Mieville (Team member) Ph.D. Physical Chemistry, 1964, University of Western Ontario, Canada, Thesis: Photo-Addition of
Methyl Mercaptan to Olefins ARIC Chemistry, 1953, Northern Polytechnic London University, England Experience: 1964-1992: Amoco Oil Research and Development Associate Research Scientist Worked on a variety of projects including combustion kinetics, oil additives and catalysis, petroleum
processes, adsorption, and inorganic membranes. The catalytic work involved all aspects of catalysis
including reaction kinetics, coke and poisoning deactivation, synthesis and characterization and
assessment of adsorbent and catalytic materials. 1954-1961: British Petroleum Research and Development Research Chemist Member of the ACS, RSC (Royal Society of Chemistry), NATAS (Thermal Society), and the Catalysis
Society of North America. Chairman of Surface Acidity Task Group of D.32 Committee ASTM 6 Patents, 25 Publications Publications: 1. D. M. Graham, R. L. Mieville, R. H. Pallen, and C. Sivertz, "Photo-Initiated Reactions of Thiols and
Olefins, I. The Thiyl Radical Catalyzed Isomerization of Butene-2 and 1,2-Ethylene-d2," CANADIAN
JOURNAL OF CHEMISTRY, Volume 42 (1964). 2. D. M. Graham, R. L. Mieville, R. H. Pallen, and C. Sivertz, "Photo-Initiated Reactions of Thiols and
Olefins, II. The Addition of Methanethiol to Unconjugated Olefins," CANADIAN JOURNAL OF
CHEMISTRY, Volume 42 (1964). 3. R. L. Mieville and Garbis H. Meguerian, "Mechanism of Sulfur-Alkyllead Antagonism," IND. & ENG.
CHEMISTRY, Volume 6, No. 4, December 1967. 4. R. L. Mieville "Measurement of Microporosity in the Presence of Mesopores," JOURNAL OF
COLLOID & INTERFACE SCIENCE, Vol. 41, No. 2, November 1972. 5. R. L. Mieville "Measuring Acidity by Temperature-Programmed Desorption," JOURNAL OF
CATALYSIS 74, 196-198 (1982). 6. R. L. Mieville "Studies on the Chemical State of Cu during Methanol Synthesis," JOURNAL OF
CATALYSIS 90, 165-172 (1984). 7. R. L. Mieville "Platinum-Rhenium Interaction: A Temperature-Programmed Reduction Study,"
JOURNAL OF CATALYSIS 87, 437-442 (1984). 8. H. Deligianni, R. L. Mieville, and J. B. Peri, "State of Pd in Active Methanol Synthesis Catalysts,"
JOURNAL OF CATALYSIS 95, 465-472 (1985). 9. B. L. Meyers and R. L. Mieville, "Reducibility of Ni-W Hydrocracking Catalysts," APPLIED
CATALYSIS, 14 (1985) 207-213. 10. R. L. Mieville, "Coking Characteristics of Reforming Catalysts," JOURNAL OF CATALYSIS 100,
482-488 (1986). 11. R. L. Mieville, "The Chemical State of Copper during Methanol Synthesis," JOURNAL OF
CATALYSIS 97, 284-286 (1986). 12. R. L. Mieville, "N2 Adsorption Method for Measuring Certain Acid-Base Sites on Alumina,"
JOURNAL OF CATALYSIS 105, 536-539 (1987). 13. David F. Tatterson and Rodney L. Mieville, "Nickel/Vanadium Interactions on Cracking Catalyst,"
I&EC RESEARCH (1988), 27, 1595. 14. R. L. Mieville and M. G. Reichmann, "Temperature-Programmed Desorption Study of CO on Pt-Reforming Catalysts," AMERICAN CHEMICAL SOCIETY (1989). 15. R. L. Mieville, "Coking Kinetics of Reforming," CATALYST DEACTIVATION (1991). 16. B. L. Meyers, R. S. Kurek, and R. L. Mieville, "Microchemisorrption," JOURNAL OF CATALYSIS,
Volume 127, No. 2, (February 1991). 17. R. L. Mieville, presentation at the Symposium on Effect of Pore Size on Catalytic Behavior
Presented before the Division of Petroleum Chemistry, Inc., American Chemical Society in Miami
Beach on September 10-15, 1976, entitled "Temperature-Programmed Desorption Studies of
Cracking Catalysts. Relationship with Microporosity and Activity." 18. R. L. Mieville, presentation at the Symposium on Multimetallic Catalysts Presented before the
Division of Petroleum Chemistry, Inc., American Chemical Society in Seattle on March 20-25,
1983, entitled "Platinum-Rhenium Interaction: A Temperature-Programmed Reduction Study." 19. R. L. Mieville, presentation at the Symposium on Zeolite and Shape Selective Catalysis Presented
at the AIChE Annual Meeting in Houston on March 29-April 2, 1987, entitled "Interacrystalline
Zeolite Diffusion." 20. R. L. Mieville and M. G. Reichmann, presentation at the Symposium on Preparation and
Characterization of Catalysts Presented Before the Division of Petroleum Chemistry, Inc.,
American Chemical Society, Los Angeles Meeting on September 25-30, 1988, entitled
"Temperature-Programmed Desorption Study of CO on Pt Reforming Catalysts." 21. R. L. Mieville, D. M. Trauth, and K. K. Robinson, General Papers (Poster Session) Presented
Before the Division of Petroleum Chemistry, Inc., American Chemical Society in Miami Beach on
September 10-15, 1989, entitled "Asphaltene Characterization and Diffusion Measurements." 22. R. L. Mieville, D. M. Trauth, and K. K. Robinson, presentation at the Symposium on Convection
and Diffusion in Porous Catalysts at the AIChE Annual Meeting in San Francisco on November 5-10, 1989, entitled "Asphaltene Characterization and Diffusion Measurements." 23. B. L. Meyers and R. L. Mieville, "A Comparative Study of TGA and TPR on Ni-W Hydroprocessing
Catalysts," (Paper # 111, ACS Meeting). 24. H. Deligianni, R. L. Mieville and J. B. Peri, "Possible Relationships of Sites for CO Adsorption with
Methanol Synthesis Activity of Supported Pd Catalysts." Patents: 1. R. L. Mieville, "Improvements in or Relating to the Production of Oxygenated Organic Compounds,"
US 882,863. 2. R. L. Mieville, "Middle Distillate Fuel Oil Compositions Having Improved Pumpability," US
3,807,975. 3. R. L. Mieville, "Middle Distillate Fuel Oil Compositions Having Improved Pumpability," US
3,807,990. 4. R. L. Mieville, "Catalyst for Selective Hydrocracking of Alkylbenzenes," US 4,171,290. 5. R. L. Mieville, "Reforming with a Catalyst Comprising Iridium, Zirconia, and Alumina," US
4,297,205. 6. R. L. Mieville, "Methods to be Used in Reforming Processes Employing Multi-Metallic Catalysts,"
US 4,048,058. j. Facilities/Equipment Mega-Carbon has their laboratory and corporate offices in St. Charles, IL. The research facilities provide
a full service organization in which all resources are under one roof: chemical engineering, computer
technology, process assembly, and maintenance. Additionally Mega-Carbon has a full complement of
chemical research equipment including UV spectrometers gas chromatographs, analytical balances,
temperature controllers, furnaces, and test rigs. Mega-Carbon recently completed research on an
improved drinking water carbon for the Environmental Protection Agency through a Phase I SBIR grant.
Additionally Mega-Carbon is located near Northwestern University, in Evanston IL, where it is possible to
have analyses run on the adsorbents to determine surface area, examine its microstructure via scanning
microscopy, and measure its adsorption capacity. k. Consultants Formal consultancies will not be used in Phase I. l. Similar Grant Applications, Proposals, or Awards No prior, current, or pending support for proposed work. References 1. D.L. Klass, in Kirk-Othmer "Concise Encyclopedia of Chemical
Technology", John Wiley and Sons, New York, 1985, p. 537.
2. Klass, D.L., G.H. Emert Eds., Fuels and Biomass from Wastes",
Ann Arbor Publications, Ann Arbor, MI, 1981.
3. Soltes, E.J., T.J. Elder, in "Organic Chemicals from Biomass",
I.S. Goldstein, ed., CRC Boca Rotan, FL, 1981, p. 63.
4. K. Nikkah, N.N. Bakhshi, D.G. MacDonald, Energy Biomass Wastes,
5. Ananth, K.P., M. Golembiewski, H.M. Freeman, in "Biomass
Conversion Processe s for Eergy and Fuel". S.S. Sofer, O.R.
Zaborsky, eds, Plenum, N.Y., 1981, pp. 173-186.
6. Elliot, D.C., in Klass and Emmet, Reference 2, p. 435ff.
7. R.L. Eager, J.F. Mathews, J.M. Pepper, H. Zohdi, Can J Chem,
8. D.L. Klass, IGT "Energy From Biomass Wastes X" Symposium
(4/7/86) Proceedings, 9. D. Gray, M. Tomlinson, ACS Div Fuel Chem., 10. J.G. Gatsis, ACS Div. Fuel Chem. Prepr., 11. R.H. Schlossberg in "Fuel Science and Technology", Ed. By
J.G. Speight, Marcel Dekker Inc., New York, 1990.
12. S.A. Foudra, J.F. Kelly, J.M. Rahimi, Energy Fuels 13. C.W. Curtiss, WlJ. Chung, Energy Fuels 14. A.V. Cugini, R.G. Lett, I. Wender, Energy Fuels 15. D.F. McMillen, R. Malhotra, D.S. Tse, Energy Fuels 16. K. Ceylan, L.M. Stock, Energy Fuels 17. M.M. Taghiei, F.E. Huggins, G.P. Huffman, ACS Div Fuel Chem
Prepr., 18. L.L. Anderson, W. Tuntawiroon, ACS Div Fuel Chem Prepr., 19. M.M. Ibrahim, M.S. Seehra, ACS Div Fuel Chem Prepr., 20. 20. W. Dolkameyer, U. Lenz, K. Theis, Erdol Kohle Erdgas 1989, 75, 79, 81.
21.H. Jung, H.W. Tierney, I. Wender, ACS Div Fuel Chem Prepr., 1993, 38(3), 880.
22. J.J. Cummins, D.A. Sanchez, W.E. Robinson, ACS Div. Fuel Chem. 1976, 21, 94.
23. A. Del Bianco, G. Del Piero, S. Serinellini, Fuel 1988, 67, 874.
Addition of base remarkably enhances
the activity. The rather simple product slate constrasts with the observations of Siskin et al 41 42 which
would suggest a more complex product mixture. The strong dependence of conversion on the catalyst
type points to a metal-organic pathway which would provide another alternative to simple ionic or radical
products. From XPS results, ruthenium was recovered as an hydrous oxide mainly in the III state and
other salts presumably presumably follow a similar course in SC water. The reaction course appears
consistent with dehydraogenation of alcohol to aldehyde and hydrogenation of olefin to paraffin as slow
steps in the sequence. This would further be consistent with soluble metal alkoxides being key
intermediates in the process. Although speciation in the WCR are not known, alcohol dehydrogenation
via alkoxide is has been recorded (62). The activity enhancement at high pH would accord with such
intermediates. Coal solubilization using metal alkoxides reported by Stock (63) supports this view. Reports
of coal (64) and shale (65)
Coals (Utah HVba), type I shale (Green River), and Athabasca bitumen will be used
in the proof of concept experiments. Mono and disaccharides, cellulose, and pulped paper will be used
as "donor" sources. Water will generally be used in 3/1 weight excess; the water charge will be designed
to nearly fill the system at reaction temperature. The system will be de-aereated prior to heating. We
will measure gas (weight loss, GC), liquid (weight,
GC, IR, Oil-Resin-Asphaltene for synfuel feeds),
and solids (weight, extractables, ash, elemental
analyses as warranted) to determine conversions
and products.
27. R.K. Sharma, E.S. Olson, ACS Div. Fuel Chem. Prepr. 1992, 37, 902. 28. D.S. Ross et al, Fuel 1984, 63, 1211; Energy Fuels 1987, 1, 287, 292. 29. Y. Watanabe, H. Yamada, N. Kawasaki, K. Wada, T. Masudo, Chem. Lett. 1992, 111. 30. Y. Takemura, H. Itoh, K. Ouchi, Ind. Chem. Eng. Fund. 1981, 20, 94. 31. I.T. Horvath, M. Siskin, Energy Fuels 1991, 5, 993. 32.W.H. Wiser, L.L. Anderson, Ann Rev Phys Chem, 1975, 26, 353, and references therein. 33.Chum, H.L., M.M. Baizer, "Electrochemistry of Biomass and Derived Materials". ACS Monograph 183, Washington, DC, 1985, pp 48-66. 34.D. Yu, M. Aihara, M.J. Antal, Energy Fuels, 1993, 7, 574. 35. P.M. Molton, R.K. Miller, ACS Symposium Series, 1981, 144, 137. 36. J.D. Cotton, J.C. Penrose, P.R. Wells, Fuel 1982, 61, 873. 37. U. Schuchardt, F.A.P. Matos, Fuel 1982, 61, 106. 38. D.G. Boocock, K.M. Sherman, J. Chem. Eng. 1985, 63, 627. 39.T.B. Thomason, M. Modell, Hazardous Waste, 1, 453. 40.M. Modell, R.C. Reid, S. Amin, US Patent 4,113,446, 1978. 41.C.J. Rogers, A. Kornel, H.L. Sparks, US Patent 5,064,526,1991. 42. E.U. Franck, Pure Appl. Chem. 1974, 38, 449; 1981, 53, 1401; 1985, 57, 1065; 1987, 59, 25: J. Chem. Thermodynamics 1987, 19, 225. 43. J.F. Connolly, J. Chem. Eng. Data 1966, 11(1), 13. 44. M.E. Paulitis, V.I. Krukonis, R.T. Kurnik, R.C. Reid, Rev. Chem. Eng. 1983, 1, 179. 45. K. Johnston, in Kirk-Othmer "Concise Encyclopedia of Chemical Technology", John Wiley and Sons, New York, 1985, p. 1141. 46. J.D. McCollum, L.M. Quick, U.S. Patent 3,983,027, Sept. 28, 1976.
47. J.D. McCollum, L.M. Quick, U.S. Patent 4,151,068, April 24, 1979; U.S. Patent 4,005,005, June 25, 1977. 48. B.D. Blaustein, M.A. Mikita, ACS Div. Fuel Chem. Prepr. 1985, 30(2), 359. 49. M.L. Swanson, E.S. Olson, J.W. Diehl, S.A. Farnum, ACS Fuel Chem, Div. Prepr. 1986, 31, 43. 50. Lilin Li, N.O Egiebor, Energy Fuels 1002, 6, 35. 51. J.A. Reuther, J.A. Mima, R.M. Kornosky, B.C. Ha, Energy Fuels 1987, 1, 198. 52.M.D. Lewan et al, Science 1979, 203, 897; ACS Div Fuel Chem Prepr. 1992, 37*4), 1545, `1643. 53. M.T. Klein et al, Fuel, 1985, 64, 635; Ind. Eng. Chem. Res., 1988, 27, 143. 54. T.J. Houser et al, Fuel 1986, 65, 827; Ind. Eng. Chem. Res. 1992, 31, 2456. 55. M.A. Mikita et al, ACS Fuel Chem. Prepr. 1988, 33(3),292; 1986, 31(4), 56. 56. D.S. Ross, ACS Div. Fuel Chem. Prepr. 1992, 37(4), 1555; Org. Geochem. 1992, 18, 79. 57. M.Siskin, A.R. Katritzky, Science 1991, 254, 231. 58. M. Siskin, A.R. Katritzky, et al, Energy Fuels 1990, 4, 475, 482, 488. (Three papers mainly on aliphatic chemistry in water at elevated temperature.) 59. A.R. Katritzky, M. Siskin, et al, Energy Fuels 1990, 4, 493 et seq (a series of eighteen papers). 60. J.D. McCollum, L.M. Quick, U.S. Patent 3,960,706, June 1, 1976. 61.J.D. McCollum, L.M. Quick, U,S. Patent 3,983,028,Sept. 28,1976. 62.J.P. Collman, L.S. Hegedus, J.R. Norton, R.G. Finke, "Principles and App;ication of Organotransistion Metal Chemistry", Univ. Science Books, Mill Valley, CA, 1987, p. 60 and references therein. 63.K. Chatterjee, S. Jiralerspong, L.M. Stock, ACS Div Fuel Sci prepr.,1992, 37(2), 1012. 64. E.S. Olsen, M.L. Swanson, ACS Div. Fuel Chem. Prepr. 1986, 31, 64. 65. S.L. Chong, J.F. McKay, Fuel Sci. Technol. Int. 1987, 5, 513.